Vibrational spectroscopy of 3,4-difluorocyclobutenes: cis-d0, trans-d0 and trans-d4 species

Infrared and Raman spectra were recorded for cis-3,4-difluorocyclobutene (cDFCB) and trans-3,4-difluorocyclobutene-d4. Unscaled density functional theory (DFT) calculations of frequencies and intensities at the B3LYP/6-311++G(d,p) level supported the complete assignment of the vibrational fundamentals. The previous assignment of fundamentals of trans-3,4-difluorocyclobutene was revised. An unusual blue shift occurs for the methylenic CH-stretching frequencies of cis-3,4-difluorocyclobutene in going from the gas phase to the liquid phase. This hydrogen bond effect is related to similar observations recently reported and interpreted. The blue shift does not occur for the vinylic CH bonds of the cis isomer and does not occur for either type of CH bond in the trans isomer.     

Factors affecting the endo : exo ratio in diels-alder reactions of cyclopentadiene

The ratio of endo-CHO:exo-CHO in the Diels-Alder addition of a trans-αβ-unsaturated aldehyde to cyclopentadiene can be changed from 1:2 to 8:1, depending on temperature and BF₃-catalysis.     

Alcohols,ethers, carbohydrates,and related compounds. II. The anomeric effect

The anomeric effect has been studied for a variety of compounds using the MM4 force field, and also using MP2/6-311++G(2d,2p) ab initio calculations and experimental data for reference purposes. Geometries and energies, including conformational, rotational barriers, and heats of formation were examined. Overall, the agreement of MM4 with the experimental and ab initio data is good, and significantly better than the agreement obtained with the MM3 force field. The anomeric effect is represented in MM4 by various explicit terms in the force constant matrix. The bond length changes are accounted for with torsion-stretch elements. The angle changes are accounted for with torsion-bend elements. The energies are taken into account with a number of torsional terms in the usual way. A torsion-torsion interaction is also of some importance. With all of these elements included in the calculation, the MM4 results now appear to be adequately accurate. The heats of formation were examined for a total of 12 anomeric compounds, and the experimental values were fit by MM4 with an RMS error of 0.42 kcal/mol.     

Facility location in the presence of forbidden regions,I: Formulation and the case of Euclidean distance with one forbidden circle

A constrained form of the Weber problem is formulated in which no path is permitted to enter a prespecified forbidden region $\text{R}$ of the plane. Using the calculus of variations the shortest path between two points $\text{x}\text{,}\text{y}\text{?}\text{R}$ which does not intersect $\text{R}$ is determined. If $\text{d(}\text{x}\text{,}\text{y}\text{)}$ is unconstrained distance, we denote the shortes distance along a feasible path by $\text{d}\text{(}\text{x}\text{y}\text{)}$. The constrained Weber problem is, then: given points $\text{x}{}_{\mathrm{j}}\text{?}\text{R}$ and positive weights w_j, j = 1,2,…,n, find a point $\text{x}\text{?}\text{R}$ such that

$\text{f(}\text{x}\text{)=}\text{Σ}\text{n}\text{j=1}\text{d(}\text{x}\text{,}\text{x}{}_{\mathrm{j}}\text{)}$

is a minimum.An algorithm is formulated for the solution of this problem when $\text{d(}\text{x}\text{,}\text{y}\text{)}$ is Euclidean distance and $\text{R}$ is a single circular region. Numerical results are presented.     

Approximation of operators with reproducing nonlinearities

We consider an equation of the form Au+N(u)=u in a Hilbert space and assume that the nonlinearity N is reproducing relative to a known sequence of vectors. Under this assumption the Rayleigh-Ritz-Galerkin approximations lead to a simple class of nonlinear algebraic eigenvalue problems.In a general variational case we show that Lusternik-Schnirelmann critical values of Rayleigh-Ritz-Galerkin problems provide upper bounds to those of the original problem. Lower bounds are constructed in the case N(u)=B^*(Bu)³.The author would like to thank the European Research Office for their assistance in this research.     

SILYL- AND GERMYL-DIAZADIPHOSPHETIDINES

Abstract

Reaction of the 1,3,2,4-diazadiphosphetidine, trans-[C₆H₅N(H)P(S)NC₆H₅]₂ with LiR (R = Me, n-Bu) followed by treatment of the resulting dianions with Me₃SiCl and Me₃GeBr produced trans-[C₆H₅N(R)P(S)NC₆H₅]₂(R = Me₃Si, 2; Me₃Ge, 3). Substitution occurs without cis-trans isomerization or significant cleavage of the 1,3,2,4-diazadiphosphetidine ring. 2 and 3 have been characterized by spectral (¹H and ³¹P NMR, IR, and MS) and elemental analytical data. Analogous reactions involving Me₃SnCl yield mixtures containing [C₆H₅N(SnMe₃)P(S)NC₆H₅]₂ which could not be isolated or completely characterized.     

Proposed Participation of Excited Monomer in the Free Radical-Catalyzed High Pressure,High Temperature Polymerization of Ethylene

The radiation-induced copolymerization of ethyl vinyl ether with dibutyl maleate was investigated over a wide range of comonomer compositions, dose rates, and in the temperature range from ?25 to 75° C. Both the rates of copolymerization and the molecular weights of the resulting copolymers were found to depend strongly on the initial comonomer composition, both reaching a maximum value at an equimolar comonomer composition. A copolymer was obtained in which the co-monomers alternate with regularity along the polymer chain over the entire range of comonomer compositions investigated. The monomer reactivity ratios were determined and found to be practically zero. The apparent activation energy was found to change at 35° C, the boiling point of the ethyl vinyl ether, from a value of 10.48 kJ/mole to a value of 18.86 kJ/mole above this temperature. This phase change also resulted in a marked decrease in the molecular weights of the copolymers formed above 35° C. The dose-rate dependence of the rate of copolymerization was found to be 0.70 over the dose-rate range     

Donor-Acceptor Complexes in Copolymerization. XLIV. Copolymerization of Styrene and α-Methylstyrene with Acrylic and α-Substituted Acrylic Esters in the Presence of Aluminum Compounds

Abstract

The copolymerization of styrene (S) with methyl acrylate (MA) and with methyl methacrylate (MMA) in the presence of AlEt₃ yields equimolar, alternating copolymers while no polymer is formed in α-methylstyrene (MS)-MA and MS-MMA systems. In the presence of AlEt_1.5Cl_l,5 (EASC), S-MA and S-MMA yield alternating copolymers, S-methyl a-chloroacrylate (MCA), MS-MA and MS-MMA yield a mixture of alternating and cationic polymers, and MS-MCA yields cationic polymer only. In the presence of A1C1₃, S-MA and MS-MA yield a mixture of alternating and cationic polymers and S-MMA and MS-MMA yield cationic polymer only. The cotacticity distributions of the alternating S-MA and S-MMA copolymers prepared in the presence of AlEt₃, EASC, and A1C1, are the same; the coisotactic, co-heterotactic, and cosyndiotactic fractions being approximately in the ratio 1:2:1. The cosyndiotactic fractions of the alter-nating copolymers prepared in the presence of EASC are in the order MS-MMA > MS-MA > S-MCA > S-MMA=S-MA.     

A cytotoxic dimeric furanoheliangolide from Piptocoma rufescens

A new sesquiterpene lactone, rufescenolide C (1), the first furanoheliangolide dimer, was isolated from the leaves of Piptocoma rufescens, collected in the Dominican Republic. Its structure was determined by interpretation of its spectroscopic data, with the absolute configuration being established by analysis of the CD spectrum. A plausible biogenesis of this dimer is proposed. This compound showed potent cytotoxicity with an IC₅₀ value of 150 nM, when tested against HT-29 human colon cancer cells.     

Protected nodes and the collapse of Fermi arcs in high-T{c} cuprate superconductors

Angle resolved photoemission on underdoped Bi2Sr2CaCu2O8 reveals that the magnitude and d-wave anisotropy of the superconducting state energy gap are independent of temperature all the way up to T{c}. This lack of T variation of the entire k-dependent gap is in marked contrast to mean field theory. At T{c} the point nodes of the d-wave gap abruptly expand into finite length "Fermi arcs." This change occurs within the width of the resistive transition, and thus the Fermi arcs are not simply thermally broadened nodes but rather a unique signature of the pseudogap phase.